Conversion of hydrocarbons



i101!- comprises may be present 4 Patented June 6, 1944 um'rso STATES PATENT OFFICE convnasrou o zi i ziiaocannom Chicago, 111., and Arthur M.

,Brooka Field, Tex, asaignors to .Upiversal Oil Products Company, Chicago, 111., a

corporation of Delaware Drawing. Application June 11, 1942,

a Serial No. 441,450

residual fractions of erals such as bauxite, hydrargiliite, or-gibbsite which are preferably heated to dehydrate them to a point at least corresponding to the mono hydrate before they are used. 'The temperadesirable decomposition reactions and produce increased yields 01 the desired low boiling trac tions.

The art of destructive hydrogenation oi hydrocarbons to produce lower boiling fractions has been practiced not only on solid hydrocarbonaceous materials such as coals and shales but. has also been practiced on the heavier liquid hydrocarbon fractions resulting from the primarydistillation of crude petroleum and the primary distillation of solid carbonaceous substances. These conversions have been effected both with and without catalysts but as a general rule better results are obtained in respect to the yield of light products when .catalysts'have been employed to increase the rate of the conversion reactions and permit the use of more moderate temperatures and pressures. The present process .is concerned with the use of special catalysts ind processes.

In one specific embodiment the present invena process for the destructive hydrogenation of heavy hydrocarbonaceous materials to produce fractions of lower boiling range therefromwhich comprises heating the hydrocarbonaceous materials under hydrogen pressure in the presence of alumina and hydrogen halides.

tructive hydrogenation ture necessary for heating hydrated aluminas to produce this degree of hydration is generally between about 400 and about 600 C., andthe invention comprises not onlythe use of precalcined natural minerals but also aluminas prepared by similar dehydration of hydrated aluminas precipitated from solutions or aluminum salts by the addition of alkaline precipitants such as, for example, ammonium hydroxide or ammonium carbonate. Satisfactory eiiects may be obtained with aluminas prepared from diflerent sources but the efliciency will vary with the source of the material, its degree of dehydration and its physical condition.

' In the operation or the process the conversions may be brought about by the so-called batch procedure in which hydrocarbonaceous material is mixed in a pressure vessel with finely divided coal 'or heavy oils such as, coal tar or petroleum distillates or residues, the requisite amount 0! hydrogen chloride and hydrogen is added and the vessel heated under pressure until the desired conversions are eflected.

' Continuous operations may be conducted by passing heavy hydrocarbon mixtures through beds or prepared alumina along with hydrogen and hydrogen chloride with proper proportioning 1-01 the reactants and the use of suitable rates 01 the present invention are an improvement over those previously used in destructive hydrogenation processes in that the components are not ailected, as are many other types of catalysts employed in similar reactions, by sulfur which in the charging stocks. Alternatively, with alumina, other 'oxides of a refractory character may be used such as zirconium oxide, thorium oxide and others. The hydrogen halides which may be used alternatively include hydrogen chloride, hydrogen drogen iodide. Obviously, when using diflerent combinationsoi oxides and halides, exactly similar catalytic eflects are not to be anticipated.

Alumina is readily available iromnaturalmin- 0. bromide and hyflow which correspond to the desired conversion. The alumina in such casesmay 'be inthe form of irregularly shaped granules or in the tom of particlesof regular shape and size such as those produced by extrusion or pelleting methods. I

The temperatures employed in eiiecting conversions in accordance with the present process may include those from about 200 to about 600 0., though usually they will be between about 350 and about 400 C. Pressures or from i to about atmospheres and any suitable excess of hydrogen may be employed which may be necessary to'give the most efiicient conversion with. the lowest yieldsoi undesirable decomposition products. Hydrogen chloride may be employed in amounts of from about 0.5 to about 50 per cent by-weight of the alumina.

The following data are introduced to indicate the type of results obtainable in destructive hydrogenation reactions'when using catalysts of the present type although it is not intended that the scope of the invention be correspondingly limited One hundred parts by weight or a Pennsylvania sas 011 containing no hydrocarbons boiling in'the gasoline range were placed in a pressurevessel and 10 parts by weight of aluminum oxide was added. Three parts by weight of hydrogen chloride was then added under presure and hydrogen was introduced to an initial pressure of 100 atmospheres. The contents of th pressure vessel were then heated to 400 C. and maintained at this temperature for a period of 4 hours, after which the vessel was cooled and the gaseous reaction products released. Bythis procedure there were produced 89' parts by volume of normally I liquid hydrocarbons and 3 parts by volume of nor mally .gaseous hydrocarbons condensible at +78! C. at ordinary atmospheric pressure. The recovcarbonaceous materials to produce lower boilinit hydrocarbons therefrom which comprises destructively hydrogenating said material in the presence of added hydrogen chloride and alumina.

2. A process for the treatment of heavy hydrocarbonaceous materials to produce lower boiling hydrocarbons therefrom which comprises 'destructively hydrogenating saidmaterial. in the.

presence of added hydrogen chloride and bauxite.

3. 'A process for the treatment of heavy hydrocarbonaceous materials toproduce lower boiling hydrocarbons therefrom which comprises destrucassasss tivelyhydrosenatiuzsaidmaterialinthepresmce ofaddedhydrosenchlorldeandapartiallydehydratedahnninapreparedbyheatingahydratcd aluminum oxide at a temperature of from about t 400 toahout 600 C.'- t

4. A process for the treatment vof heavy petrole'um fractions to produce gasoline therefrom which comprises destructively hydrogenating said fractions-in the presence of added hydrogen chloride and alumina.

5. A process for the treatment of heavy pe- -troleum fractions to produce-gasoline therefrom which comprises destructively hydrogenating said fracflons in the presence of added hydrogen chloride and bauxite. a

6. A process for the treatment of heavy peerefrom troleum fractions to produce gasoline th which'comprises destructively hydroyenatin: said fractlonsinthe presence oraddedhydrosenchloride and a partially dehydrated aluminam'ewod byheatincahydratedaluminumoxideatatem peratureoffromaboutiwtoahoutiiov C.

I. A process for the treatment of heavy hydrocarbonaceous materials to produce lower boilins hydrocarbons therefrom which comprises destructively by said material at a temdmenating perature of from about 200toabout 600' O.under aninitial pressure notsubstantiallyinexcessof 100 atmospheresinthepresenceof addedhydrogen chloride and alumina, the amount of hydro- .genchlorldebeinlfromaboutoltoabdutw of the alumina.

LOUIS BCBMERLING. ARTHUR H. DURJNBEI.

per cent by weight 

